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A BSTRACT. These are notes and solutions to Kittle and Kroemers Thermal Physics. The solutions are (almost) complete: I will
continuously add to subsections, before the problems in each chapter, my notes that I write down as I read (and continuously reread).
I am attempting a manifold formulation of the equilibrium states in the style of Schutzs Geometrical Methods of Mathematical
Physics and will point out how it applies directly to Thermal Physics. Other useful references along this avenue of investigation is
provided at the very bottom in the references.
Any and all feedback, including negative feedback, is welcomed and you can reach me by email or my wordpress.com blog.
You are free to copy, edit, paste, and add onto the pdf and LaTeX files as you like in the spirit of open-source software. You are
responsible adults to use these notes and solutions as governed by the Caltech Honor Code: No member of the Caltech community
shall take unfair advantage of any other member of the Caltech community and follow the Honor Code in spirit.
S ECOND E DITION. Thermal Physics. Charles Kittel. Herbert Kroemer. W. H. Freeman and Company. New York.
QC311.5.K52 1980 536.7 ISBN 0-7167-1088-9
g1
U1
g2 dU + g1
N1
g2
U2
dU2 = 0
N2
EY : 20150821 This step can be made mathematically sensible by considering the exterior derivative d of g C (), where
is the manifold of states of the system, with local coordinates N, U , where U happens to be a global coordinate. Then,
1
U1
=
N1
2
U2
N2
Temperature. T1 = T2 - temperatures
of 2 systems in thermal equilibrium are equal.
[?].
T must be a function of U
N
1
=
= kB
T
U N
Experimentally, kB = 1.381 1023 J/K = 1.381 1016 ergs/K.
Now
1
=
= kB T
U N
Problems. Solution 1. Entropy and temperature.
3N
log U
2
3N 1
1
3N
=
= = U =
U
2 U
2
(b)
2
U 2
N
<0?
2
U 2
=
N
3N
2
1
U2
<0
Solution 2. Paramagnetism.
U
2mB
U 2
2(mB)2 N
U2 1
where 0 = ln g(N, 0)
2m2 B 2 N
U 1
1
=
= 2 2
U N
m B N
What is the thermal equilibrium value of this N -spin system of fractional magnetization? If U denotes hU i, thermal average
energy, we also get the thermal average spin excess.
hU i = h2mBsi = 2mBhsi
= =
m2 B 2 N
mBN
=
U
2hsi
(N +n1)!
n!(N 1)! .
+n)!
+ 1, n) = (Nn!N
! .
(N + n)!
= ln (N + n)! ln (n!) ln (N !)
n!N !
(N + n) ln (N + n) N n n ln n + n N ln N + N = (N + n) ln (N + n) n ln n N ln N
(N + 1, n) ln g(N + 1, n) = ln
U
U
U
U
) ln (N + ) ln N ln N
U N .
1
1
U
1 U
1
= ln (N + ) ln = ln
N
N
+ 1 or U =
U
exp (/ ) 1
10 keys
second
10 keys
second
1 hamlet
5
10 characters
= 1018 s
= 1019 keys
= 1024 possible Hamlets
From part (a), the probability that a given, random sequence is Hamlet, 10164345
(1029 characters)(10164345 ) = 10164316
164345
Note, I think that the probability should be (1029 characters) 1015 Hamlet
) = 10164321
characters (10
5
Since we are considering the number of Hamlet, 10 character sequences.
3. B OLTZMANN D ISTRIBUTION AND H ELMHOLTZ F REE E NERGY
cf. Example: Energy and heat capacity of a two state system, pp. 62 of Kittel and Kroemer [1]. Kittel and Kroemer
introduces the heat capacity very early, specific to this example.
Definition 1. heat capacity CV at constant volume is defined as
(1)
CV :=
V
Recall the thermodynamic identity (which is introduced many equations later):
dU = d pdV 1 ()
where is a manifold of states of all systems.
i.e. no component
Consider local coordinates of , (, V ). Consider curve c : R s.t. c generates a vector field c =
c( )
in the V direction. Notice the prescient choice of parameter .
Now for internal energy U C (), taking the exterior derivative d results in
dU =
U
U
d +
dV
dU
U
=
+0
Now,
=
=
V
Hence,
(2)
CV :=
=
V
V
EY: 20150825 Why do we need differential geometry? Its because I always wondered why you could do this:
U
?
?
CV :=
=
with d = dU = = U
V
V
and talk of differentials.
Definition: Reversible process. EY : 20150824 Mathematically, 1-forms are exact.
3
W (c)
= pV = dU (c)
=
= p =
(3)
U
V
U
V
Consider another set of coordinates (U, V ) for manifold . Now entropy is a function of U, V , as = (U, V )
C (M ), so
that
d = U
dU + V
dV
V
U
U+
V
d(c)
=0=
U V
V U
Now define
Definition 2.
1
:=
(4)
V
So then we have 1 U + V U V = 0. For the parameter of curve c, choose the parameter to be V , knowing that is constant
on this curve, or thermodynamic process. Thus
1 U
p
=
=
=
or
V
V U
V U
(5)
p=
U
Thermodynamic
Let = (U, V ) C (). Then
Identity.
d = U V dU + V U dV 1 ().
d = dU + pdV
2M L
n
(nx ,ny ,nz )
Let
2 =
~2 2
~
or =
2
2M L
(2M )1/2 V 2/d
Then
Z
dnx
Z1 =
0
Z
dny
In general, Z1 =
Now
dnz exp [
(n2x
n2y
Z
n2z )]
3
3 1/2 3 1/2 3
1
=
=
2
2
d
1/2
Z1 =
1/2 V 1/d
2 (2M~
)1/2
!d
nQ
V
= nQ V =
d/2
2~
n
1 + e/
/
e
F
=
= ln (1 + e/ ) + /
(1 + e
)
U = 2
(a) Remember to calculate the multiplicity in the N -spin system (its not enough to sum up exp (s / ) factors).
Us = M B = 2smB
M = 2sm
N = N+ + N
2s = N+ N = N+ (N N+ ) = 2N+ N
N/2
Z=
X N
2smB
=
exp
N+
s=N/2
= e
N mB
(1 + e
2mB
N/2
X
N
2
s=N/2
)N = 2N coshN
mB
N!
exp
+ s ! N2 s !
2mBs
=
N
X
s=0
N!
exp
s!(N s)!
2mB
N
s
=
2
PN
j=1
N
j
mB
mB
m
) sinh
2
mB
M = 2
ln Z = N m tanh
2
M
Nm
mB
=
=
sech2
B
Z = 2N (N )(coshN 1
(b)
For x
M
nm
mB N
mB
F = ln Z = ln (2 cosh
)
= N ln (2 cosh
)
2
N
4
2
2
= tanh mB
=
ln
.
.
Now
1
tanh
y
=
sech
y.
F
=
N
ln
2
2
1x
1x2
m2 N
X
s~0
1
= (1 e~0 / )1
Z=
exp
=
~
0 /
e
s=0
~0
~0
~0 /
F = ln Z = ln (1 e
) ' ln
for 1
(b)
~0
F
~0
~0 /
~0 /
=
(e
ln (1 e )
= {ln (1 e~0 / ) +
)
} = ~ /
~
/
0
0
1e
e
1
Solution 4. Energy fluctuations.
X
es
Z=
1
s
P
X
=
s es /
Z =
es
U= s
= ln Z
1
Z
s
=
= 2
X
2 Z =
2 es
(c) For
mB
1, cosh2
mB
1. =
U
Z
= 2 U = 2
= 2
(2 Z)Z ( Z)2
Z2
!
=
2 Z
Z
Z
2 !
=
U
= h2 i hi2
and
gR (UR ) = exp (R (UR ))
R
If dU
=
(
1)
=
U
small
compared
to
U
R
R.
d
= 2
dUR
= UR (n) + ( 1)
d
1
R (UR ((n + 1))) ' R (UR (n)) + ( 1)
exp (R (UR (n)) + 1 ( 1))
P (ES = (n + 1))
=
= exp (1 )
P (ES = n)
exp (R (UR (n)))
2
X
X
d (j 2 +j)0 /
X d 0 / j +j
j(j+1)0 /
(e
)
=
e
Z=
(2j + 1)e
=
dj
0
0 j=0 dj
j=0
j=0
UR (ES = (n + 1)) = UR (n) +
(b) For 1
0
ZR ( ) =
0
Z
0
d 0 / x
e
dx
+x
dx =
6
0 / x2 +x
(e
)
(e0 / )0 =
0
0
(c) For
0
1
ZR ( ) = 1 + 3e20 /
(d)
0
2
U =
for 1
U = ln
=
0
60 e20 /
1
20
20 /
=
for
1, U = 2
(3e
)
2
2
/
0
1 + 3e 0
1 + 3e20 /
U
0
CV =
= 1 when 1
V
2 / !
20
20 /
20 /
0
20 /
(1
+
3e
)
(3e
)
e 0
e20 / 2
1
2
2
2e
= 120
2
(1 + 3e20 / )2
(1 + 3e20 / )2
2
CV = 60
0
ln Z
1, CV 12
e20 /
( /0 )2
N
X
exp (s/ ) =
s=0
1 e(N +1)/
1 e/
(b) 1 .
PN
Z = s=0 exp (sB)
PN
1
1 s=0 (s)es
ln Z =
= hsi =
Z
1 e/
e(N +1)/ ((N + 1))(1 e/ ) (e/ )()(1 e(N +1)// )
=
=
1 e(N +1)/
(1 e/ )2
=
This still does not give the desired approximation. Consider the following:
e eN
1 e(N +1)
=
1 e
e 1
N
((e + N e
)(e 1) (e )(e eN ))
(e (e + N eN e + eN ) e N eN )
Z =
=
(e 1)2
(e 1)2
Z=
(e (N + 1)eN e N eN )
(e (N + 1)eN e+ N eN )
Z
=
'
=
N
Z
(e 1)(e e
)
e2
(N e(N 1) + e(N 1) e N eN )
((N + 1)e(N 1) (e + N eN ))
=
=
2
e2
e N
N
e
(N +1)e
N e +eeNe
(Ne+1)e
eNn e
e
N
eN
N eN
=
=
=
=
'
e2
e2
e2
eN e
'
(eN )
= e
eN e
= hsi = e/
n y
Solution 8. Quantum concentration. Now (x, y, z) = A sin nxLx sin yL
sin
Ground orbital: nx = ny = nz = 1.
3 2
3 2
T =
h0 |0 i =
2m L
2m L
7
nz z
L
. p = 1i ,
p2
2m
1
= 2m
2 .
Z L
2nx x
n x
nx sin
1
cos
x
L
dnx =
sin2
dnx =
L
2
0
2nx x
L
L
2nx
L
= L
2
0
3
L
A2 L3
8
2
h|i = A
=
= 1 or A2 = 3
2
8
L
m 3/2
Recall that nQ = 2~
.
2
Consider the condition that there will be a concentration for which the zero-point quantum kinetic energy is equal to the
temperature :
3/2
3 2 2/3
2m
3 2
2m
2/3
=
or
n
=
=
n
=
or
n
=
2m L2
2m
3 2 ~2
3 2 ~2
3/2
4
4
m 3/2
= n = (
)
=
nQ
2
3 2~
3
Solution 9.
E1+2
E1 +E2 =E0
XX
E2
E1
=
g(E1 )g(E2 ) exp
exp
= Z(1)Z(2)
E1 E2
N
2
N+ =
2s+N
2 .
2N !
+ s ! N2 s !
(b) |s| N
l
l
2(N
!)
=
(l) = ln g N,
+ g N,
= ln
l
l
N
N
2
2
+
!
+
2
2
2
2 !
L
N
l
N
l
N
l
N
l
N
l
N
+
ln
+
+
+
ln
}
= ln (2N !) = {
2
2
2
2
2
2
2
2
2
2
2
2
where we used ln(x + x) ' ln x + x1 x.
l
N
1 l
N
N
l
N
1
l
N
+
ln
+
ln
+
}=
(l) = ln (2N !) {
2
2
2
N/2 2
2
2
2
2
N/2 2
2
N
N
N
N
N
N
l
N
l
2
l
l
l
N
l2
= ln (2N !) { ln
+
ln
+
ln
+
+
+
ln
+
}
2
2
2
2
2
2
2
2
2 N 2
2
2
2
N 22
!
2N !
l2
(l) = ln
N
N
N 2
2 ! 2 !
(c)
2l
=
l
N 2
= f =
2l
N 2
~2 2 2
n =
n
in one dimension
2m L
X
~2 2 2
2 n2
Z1 =
exp
n / =
dne
=
2m
L
2
0
n=1
8
~2 2
2m L
.
where
~/L
=
2m 1/2
Recall that = F
, F = U , so that
2 =
2
2~/L
F = ln Z = N ln
= N ln
= N ln
=
2
2m 1/2
!
1
2~
2~2
= N ln
= N ln
2
mL2
mL 1/2
!
1
2~2
N
1
2~2
F
=
= N ln
+
2~2
2
mL2
2
mL2 2
mL2
1
2~2
N
N
2~2
= N ln
+
=
ln
1
2
mL2
2
2
mL2
4. T HERMAL R ADIATION AND P LANCK D ISTRIBUTION
Problems. Solution 1. Number of thermal photons.
We consider a cavity of volume V , and of edge length L (so V L3 ). So then n = nc/L.
1
is the thermal average number of photons in a single mode frequency . So then
Now exp ~
( n )1
X
X
1
hsn i =
~n
exp 1
Consider (nx , ny , nz ) on positive octant, and 2 independent polarization s of em field.
Z
Z
X
(2)
n2 dn
1
1
2
=
=
=
4n
dn
8 0
1
1
1
exp ~nc
exp ~nc
exp ~nc
0
L
L
L
n
3 Z 2
L
x dx
V 3
=
= N= 2
(2.404)
x
~c
e 1
~c
0
where I used the substitutions
~cn
L
L x
=n
~c
L
= dn
(dx)
~c
x=
1
=
N
2.404
4 4
45
' 3.602
R
2
dx
Now how was 0 dx exx 1
evaluated?
Solution 2. Surface temperature of a Sun. Given the solar constant of the Earth, the total radiant energy flux density at
the Earth from the Sun normal to the incident rays, integrated over all emission wavelengths,
solar constant = 0.136 J s1 cm2 ,
(49)
(a)
4(1.49 10
11
m) 0.136 J s
cm
102 cm
1m
2
Note that I had used 1.49 1011 m as the distance of the Earth from the Sun.
(b) J = energy flux density or rate of energy emission per unit area.
2 k4
B = 60~3Bc2 = 5.670 108 W m2 K 4 .
Note that W = 1sJ . I will use R = 6.9599 1010 cm as the radius of the Sun.
4 1026 J s1
= J = B T 4
4(6.9599 1010 cm)2
9
102 cm
1m
2
4 1026 J s1
1m
4
4
k = T
10
2
4(6.9599 10 cm)
5.670 108 J/s
T ' 5830 K
Solution 3. Average temperature of the interior of the Sun.
(a)
R
Z
U =
4
3
3 r
3GM 2
U=
5R
Z
1 RG
U =
2 0
(4r2 dr)
16
= 2 G2
r
3
4
3
3 r
r4 dr =
16 2 2
4
GR5 ; M = R3
15
3
Z
8 2 2
8 2 2 R 4
r dr =
(4r dr) =
G
GR5 =
r
3
15
0
2
8 2
3 GM 2
M
=
=
GR5 4 3
= 1.14 1041 J
15
10
R
R
3
(b) Using the virial theorem of mechanics, note that
1 kg
m2
11
33
kg sm2 kg
g 10
2 2 10
3g
1
3 GM 2
3 6.67 10
U=
=
= 5.72 1040 J
2
20 R
20
7 1010 cm 1012mcm
1
Now hsi = exp (~/
)1 , is the Planck distribution function, giving the thermal average number of photons in a
single mode frequency .
~
thermal average energy hi = hsi~ = exp (~/
)1 for ~, hi '
40
So then 5.72 10 J = N hi = N .
5.72 1040 J
= 4.14 106 K
1 1057 (1.381 1023 J/K)
1 hr
3600 s
1 day
24 hr
1 yr
365 days
4
Solution 5. Surface temperature of the Earth. JS = b T
is the radiant power per unit area.
2
Total emitted radiation energy of the sun is JS 4R
.
2
4R
JS
2
4RES
R2
X
j
j =
sj ~j
P =
j
10
X
U
j
=
sj ~
V
V
j
dj
1
1 j
=
jcV 4/3 =
dV
3
3 V
U
(c) p = 3V
(d) We want the Kinetic pressure at a concentration of (1 mol/cm3 ). Recalling P = N kVB T ,
2
3
6.022 1023
10 cm
N
1 mol
23 J
1.381
10
(2 107 K) = 1.663 1014 2
P =
cm3
1 mol
1m
K
m
U
1 2
N
4 = 4.03 1013 2
=
3V
3 15~3 c3
m
where t = 2 107 K.
For the pressures to be equal,
1 2
N kB
45(~c)3 N kB
4 4
kB
T =
T or T 3 =
so that T = 3.2 107 K
4V
3
3
3 15~ c
V
2 kB
Free energy of a photon gas
P
Q
1
1
Consider Z = s=0 es~/ = 1e~/
for a single mode.
(a) Z = n 1e~
n /
P
nc
~n /
(b) F = ln Z = n ln (1 e
)
n = L .
Z
Z
X
4n2 dn
(2) ln (1 e~nc/ L ) =
dnn2 ln (1 e~nc/ L ) =
F =
ln (1 e~n / ) =
8
0
0
n
Z
Z
3 ~nc/ L
n e
~c
n3
~ 2 c
= (n3 ln (1 e~nc/ L ))
dn
dn ~n/ L
=
=
~nc/
L
L
L
0
1e
e
1
0
0
3 Z
x3
( L)3 2
L
=
=
~c
ex 1
(~2 c3 ) 45
0
Solution 7.
B Tl4
+ B
Tu4 + Tl4
2
= B
Tu4 Tl4
2
Solution 9. Photon gas in one dimension. E = E0 sin (kx) cos (t) is the form of a solution with kL = n or k =
since
n
L ,
= v, n = v
k
L
1
=
1 e~/
v 2 Ex x = Et t v 2 k 2 = 2 or
Zj =
es~/
s=0
d
~n 1
~ 2
~n
1
1
s=0 se
=Z
(1 exp
) = Z (1 exp
) exp
=
hsi =
Z
d(~n / )
exp (~n / )
=
1 exp (~n / )
So
~vn/L
exp ~vn
1
exp 1
L
n
n
2
X
X ~v n2 exp ~vn
X ~v 2 n2 exp ~vn
U
~vn
~vn
~vn/L
L
L
L
L
=
=
=
2 exp
2
L
L 2
(exp ~nv
1)2
(exp ~v
exp ~vn
1
L
L n 1)
n
n
n
L
hsi~n = hn i =
~n
U=
~n
11
hn i =
R
P
Now n 0 dn for one-dimensional photon. Let = ~v
L .
Letting x = n,
Z
Z
nv 2 Z
n2 exp (n)
1
x2 ex
1
U
x2
xdx
dn n
=
dx x
= { x
=
+
}
x1
L
(e 1)2
(e 1)2
(e 1)
e
0
R
R (kx)
(kx)3
Coefficient of k term of f (k) is j = 0 exx1 dx. Now f (k) = 0 sin
ex 1 dx, sin (kx) = kx 3! + . . . , so that
Z
x
2
=
dx
x1
6
e
0
U
L 2
L
=
=
= CV
~v 6
6~v
Solution 10. Heat capacity of intergalactic space.
Given the density 1 atom m3 , considering thermal radiation at 2.9 K, then kB T = (1.381 1023 J/K)(2.9 K), ~c =
(1.05457 1034 J s)(3 108 m
s ).
2
4 2
3
Recall for radiation, that the energy per unit volume: VU = 15~3 c3 4 so that U
= 15~3 c3 V .
dU
3
3
Assume hydrogen atoms modeled as ideal gas: U = 2 N , d = 2 N .
CVmatter
=
CVradiation
3
2N
4 2
15~3 c3
3V
45(~c)3 (N/V )
= 2.8 1010
8 2 (kB T )3
exp
~n
1'1+
~n
+
~n
~n
~vn
L ;
n =
vn
L .
For ~n , 0 n nD .
2
3
1
1 ~n
+
+ 1
2
6
~n
~n
'
~n
1+
~n
2
)2
(~n
6 2
=
1+
~n
2
(~n )2
6 2
= +
~n
(~n )2
+
+ ...
2
12
For np = (6N/)1/3
Z
Z
3 nD
~n
(~n )2
3 nD
~ vn ~2 2 v 2 n2
U=
dnn2 (
+
)=
dnn2 (
+
)=
2 0
2
12
2 0
2 L
12 L2
4/3
~2 2 v 2 1 5
3 2 ~v 6N
~v n4D
6N
3~2 3 v 2 (6N/)5/3
3 1 3
{ nD
+
n
}
=
+
=
2 3
2L 4
12 L2 5 D
2
16L
120 L2
So
3 2 ~v
U = 3N
16L
Now T = , =
So then
~v
kB
6N
4/3
+
3~2 3 V 2 (6N/)5/3
120 L2
(6 2 N )1/3
L
~v(6 2 N )1/3
3 2 ~v 61/3 N 4/3 6
15 (6 2 N )1/3 ~v
15
=
=
N
k
B
4/3
L
16L
8
L
8
U
15
15
6.022 1023 particles
= N kB
=
(1.381 1023 J/K)
= 15.59
8
8
1 mol
which is very close to experimental values.
2 V
4 2 V
4
3
Solution 12. Heat capacity of photons and phonons. For a photon: U = 15~
U = 15~
3 c3
3 c3 .
3 4 N 4
U
12 4 N 3
phonon: U ( ) = 5(kB )3 .
= 5(kB )3
So then
3
12 4 1022
1
CV =
= 2.3 1018
5
100
for a phonon.
For a photon,
4 2
(1.381 1023 J/K)3
3 = 220 /K 3 3
15 (1.05457 1034 J s(3 1010 cm/s))3
U = 3N
12
2
Recall that
h( hi)2 i
12 4 N 5
=
2
hi
5(kB )3
= h( hi)2 i
V
3 4 N 4
12 4 N 3
where U =
3
5 (kB )
5(kB )3
V
!
3
20 1
1
0.068
1
1
3
=
(k
)
=
B
9 8 N 2 8
3 4
N
3
N
T
25(kB )6
s
3
0.070 200
= 0.02
F=
1015 102
(a) Given v = 2.383 104 cm s1 and accounting for only longitudinal waves (only longitudinal polarization), then the
Debye temperature is
!!1/3
1/3
1 He
~v
(1.05457 1034 J s)(2.383 104 cm/s) 18 2 0.145 g 1.00727647 u 4.0026u
18 2 N
=
=
=
kB
V
1.381 1023 J/K
cm3
1.67262 1024 g
= 28.6 K
(b) Recall the derivation for U for phonons in a solid. Account for only longitudinal waves (only longitudinal polarization).
Z
Z
Z
~ nv
nD 2
~ 2 v nD
n3
nD
n2 ~n
L
=
=
dn
U=
dn
n dn
2 0
exp (~n / ) 1
2 0
exp (x) 1
2L 0 exp (x) 1
~nv
L
With n = n
L v, x = L or ~v x = n, then
2
4 Z nD
~ v
L
x3
U=
dx
x
2L
~v
e 1
0
18N 1/3
1/3
2/3 1/3
Dv
For low temperatures, small so take xD = ~n
= ~v
= 18 ~ n v to go to .
L
L
4
2
V
U
3
2(~v)
15
2
2
3
4
Recall that CV = U
V . Then CV /V = 15 (~v)3 . Recall B = kB T , and given v = 2.383 10 cm/s, then
kB
(1.381 1023 J/K)
=
= 5.495 106 (1/K cm)
~v
(1.05457266 1034 J s)(2.383 104 cm/s)
So if we take CV /V and divide by the given density = 0.145 g/cm3 to get the heat capacity per gram, (and multiply
by kB , the Boltzmann constant to get the correct units; Kittel and Kroemer likes using dimensionless formulas ) then
3
2
kB
cm3
= 0.0208 T 3
(CV /V )/ = (kB ) 2
T3
15
~v
0.145 g
Solution 15. Angular distribution of radiant energy flux.
(a) Recall
u =
~
2 c2
exp ~
1
is the radiation energy per unit volume per unit frequency range.
cu = energy per unit time, per cross sectional area per unit frequency range.
em waves emitted spherically from pt. Q.
Suppose em wave comes in at a funny angle other than directly inward.
Consider area da thats from the spherical wave from pt. Q. How much of that goes into solid angle d?
= cu cos dA
13
So cu cos is the energy per unit time, per cross-sectional area, per unit frequency range, that enters into some solid
angle d.
r2 d
d
=
2
4r
4
is the fraction of the spectral density that if arrives in solid angle d.
d
4
is the spectral density of radiant energy flux that arrives in solid angle d.
= cu cos
(b)
Z
Z
cos sin dd = 2
sin 2
d =
2
=
/2
1 1
cos 2
=
=
2
2
0
cu
4
1
1 e~/
s=0
X
s~
~
~
~/ 2
~/
Z =
es~/
=
(1
e
)
(e
)
= Z 2 hsi
2
2
s=0
Z=
es~/ =
Then
e~/
1
hs + 1i =
~/
1e
1 e~/
~
~
Z
= ln hs + 1i + 2 hsi = ln hs + 1i +
hsi
= ( ln Z) = ln Z +
Z
hsi =
Now (nyn)
hs + 1i
hsi
hsi ln
= Ze~/ ln e~/ =
~
hsi
= = hs + 1i ln hs + 1i + hsi ln hsi
Solution 18. Isentropic expansion of photon gas.
1/3
(a) i Vi
1/3
= f Vf
or
Vi
Vf
1/3
r
r
r = r(t) = t so that r = t or
f
2.9 K
= 103
=
i
3000 K
t
t
rf ri
ri
tf ti
ti
=1
=
=1
rf
rf
tf
tf
Knwowing that
(b) Now
ri
rf
= 103 , then
ti
tf
= 103 .
= V 1/3
3
=V
2
4
4
=
U
=
V
=
3
3
3
3
4/3
V
15~ c
15(~c)
15(~c) V 1/3
V
U
2
1 4/3
4
=
V
V
15(~c)3
3
!
!
Z
4/3
Vf
2
2 4
1
1
2 Vi i4
1
f
2 Vi i3
4
1/3
(V
) =
(i f )
W = pdV =
1/3 =
=
3
3
3
1/3
1/3
1/3
15(~c)
15(~c)
15(~c)
15(~c)3
Vi
Vi
Vf
Vi
i V i
14
+Ju = b u4
Jl = b l4
= (1 r)
=
2
2
2
2
2
a(Ju + Jl )
(1 r)(Ju Jl )
b (u4 l4 )
=
+ rJl Jl =
= (1 r)
2
2
2
Jnet =
M 3/2
Recall that for ideal gas, F = [N ln Z1 ln N !]; Z1 = nQ V = 2~
V.
2
n
F
d
= [log Z1
ln N !] = ln
=
N ,V
dN
nQ
3/2
M
where nQ = 2~
2 .
R
Now = log nnQ
ext =
GMe
r
2
gRm
r
since g =
GMe
Re2 .
tot = ln (n/nQ ) + M gh
In equilibrium, this must be independent of r: tot (r) = tot (R).
M gR2
gR2 M
= ln (n(R)/nQ )
ln (n(r)/nQ)
R
2 r
n(r)
R
M g R2
n(r)
ln
= Mg
R or exp
R
=
n(R)
r
r
n(R)
M g R2
1
= n(r) = n(R) exp
r
R
so that
N = 4n(R) exp
M gR
r2 dr exp
M gR2
r
Z(, ) =
X
X
N =0 s(N )
X
ASN
15
= exp
, 1 for N = 0; for N =
0(1)+(1)(+ exp (
))
= (1+expZ(/ ))
hN i =
Z
exp (/ )
hN ()i = 0(1)+(0)()+
= exp Z(/ )
Z
exp (/ )
hi = hN ()i =
Z
(a) Z = 1 + + exp
(b)
(c)
(d)
(e)
1, + exp
. for = 0.
Z = e 2 + e 2 + e 2 + 2 e 2
Z = 0 + e/2 + e 2 + 2e 2
ln Z =
e 2 + e 2 + e 2 + 2 e 2
=1
2 e/2 = e/2
2 = e/ or 2 ln = /
2 ln =
Solution 8. Carbon monoxide poisoning.
(O2 )
9
9
(O2 )
=
A
; or ln
= (8.617 10
(O2 )
9
A
= A
eV
)(273 + 39) ln
k
105
9
= 0.3686 eV
P (O2 ) =
(O2 )eA /
= 0.1 = 0.1 + 0.1(CO)eB / = 0.9(O2 )eA /
1 + (O2 )eA / + (CO)eB /
ln
9(O2 )eA / 1
(CO)
B
=
or B = ln
(CO)
9(O2 )eA / 1
= 0.5511 eV
Solution 9. Absorption of O2 in a magnetic field. Recall that 2j + 1 = total number of spin states.
2(1) + 1 = 3.
Now U = m B.
+B B
A
(A +B B)
+ (O2 )e + (O2 )e
=
B B
Z = 1 + (O2 )eA / (1 + 2 cosh
)
(O2 )eA / (1 + 2 cosh B B )
B B
A /
0.91 =
or 0.91 = 0.09(O2 )e
(1 + 2 cosh
)
1 91 1
eA / 1 = cosh
or B =
arccosh
eA / 1
2 9 (O2 )
B
2 9 (O2 )
Z = 1 + (O2 )e
The Gibbs sum in the limit of zero magnetic field will differ from that of Problem 8 because there the spin multiplicity of the
bound state was neglected.
16
Z = 1 + 3(O2 )eA /
3(O2 )eA /
= 0.9 or 0.9 = 0.3(O2 )eA /
1 + 3(O2 )eA /
3
(O2 )
ln
= A / or A = ln
= 0.6227
(O2 )
3
for T = 300 K, so that = 0.049375 eV .
P (O2 ) =
0.049375 0.59927
0.59927 =
= 511.1 T
B
5.7884 1011 106 eV /T
Solution 10. Concentration fluctuations.
P P
(a) Recall that Z = N =0 s(N ) exp [(N s(N ) )/ ].
X N 2
2 2Z
2Z
=
exp [(N s(N ) )/ ]
hN 2 i =
2
Z 2
= B =
ASN
(b)
hN i =
,V
2
,V
Z2
+
hN i = hN 2 i hN i2 = h(N )2 i
d =
dU +
dV +
dN
U V,N
V U,N
N U,V
=
(35)
N U,V
2Z
2
,V
(31)
Consider when d = dV = 0.
=
Note that
Using the
dU
dN
U
N ,V .
definition, U
N,V
dN +
dU = 0
U V,N
dU
=
U V,N dN
1 , so then
=
U
N
,V
Likewise, =
U
N ,V
= pdV + dN d
F
=
= (, V, N )
N ,V
F
is equivalent to (, V, N ) = N
through the thermodynamic identity as well.
,V
dU = d pdV + dN
, V constant. d, dV = 0.
=
U
N
=
,V
n0 = concentration in saturated air that stands immediately above pool of water of water vapor in air.
rn0 = actual concentration of water vapor in air at uppermost leaves is rn0 .
At pool, H2 O = vapor for diffusion equilibrium.
Same condition at uppermost leaves, otherwise theres evaporation:
sap = vapor (h).
sap = H2 O (no flow going on in water). Thus, vapor (h) = vapor (0) and treat water vapor as an ideal gas.
n(0)
n(h)
+ mgh = ln
ln
nQ
nQ
rn0
1
1
ln
= mgh = ln
= mgh or h =
ln
n0
r
mg
r
2
1
10
)(298 K)(kg m
(1.381 1023 K
s2 ) ln 9
h=
= 147.1 m
27
kg
2)
(18 amu) 1.6710
(9.8
m/s
1 amu
Solution 13. Isentropic expansion.
(a)
M 3/2
V and
(b) Recall that F = [N ln Z1 ln N !] where Z1 = nQ V = 2~
2
F
= V,W .
3/2
1
F
M
3 1/2
= [N ln Z1 ln N !] [N
V]=
Z1 2~2
2
1
3
3
= [N ln Z1 ln N !] [N nQ V ] = [N ln Z1 ln N !] N
Z1
2
2
3/2 3/2
M
With N constant and Z1 = 2~
V , then for an isentropic expansion, V 2/3 must remain constant.
2
Solution 14. Multiple binding of O2 .
(a) Be wary of the multiplicity, how you count, each of the energy states.
4 2 2/
4 3 3/
Z = 1 + 4e/ +
e
+
e
+ 4 e4/ = (1 + e/ )4
2
3
P () =
4e/
(1 + e/ )4
(b)
P (4) =
4 e/
e/
=
4
/
4
(1 + e
)
1
+e/
6. I DEAL G AS
Reversible Isothermal Expansion. Q = 0, insulated gas, no heat flow to or from the gas (adiabatic)
constant in system isolated from reservoir, if expansion reverisble (slowly)
What is the pressure after expansion? Remember
Cp
=
CV
So let
5
2N
3
2N
5
=
3
3
1
=
1
2
1
(7)
(, V ) = N (ln 1 + ln V + constant )
(8)
ln 1 V = constant or 1 V constant
(9)
= 11 V1 = 21 V2
18
(63)
(61)
(62)
1
1
= 1
= 2
p1
p2
(10)
1
(64)
dp dV
+
=0
p
V
For
V 1 = i Vi1
then taking d:
d V 1 + ( 1)V 2 dV = 0 =
For
1
d
+
dV = 0
1 p = i1 pi
then taking d:
dp 1 +
21
dp
d
1 d p = 0 =
+
=0
1
p
1
p
V
=
pi Vi
= p
V
pi Vi
V
B = p
EY : 20150606 I think when one consider small, linear longitudinal perturbations of the gas system, with pressure
being the external restoring force, then sound waves propagate (correct me if Im wrong) and this is the way to derive
B .
p
isothermal bulk moduli B = V V
= n
V =p
1/2 1/2
= p
velocity of sound in gas is c = B
V
Consider applying this 1-form onto X:
1
1
d
d
dV (X) = +
V = 0 =
( V 1 ) = 0
V
d
Then the equalities of the endpoints of this curve ( (), V ()) are the equalities above. The interpretation is that the isentropic
process draws out a curve in M and can be written as a curve or as a tangent vector field (specifically a section of T M).
19
1 V11 = 2 V21
(11)
(12)
P1 = 2
P1 V1
(13)
T1 = 300 K ,
V1 /V2 =
(66)
P2
P2 V2
(67)
(68)
1
2,
2/3
1
T2 =
(300 K) = 189 K
2
(14)
(69)
(15)
(70)
1
N (2 1 )
1
1
exp [()/ ]+1
= (e()/ + 1)1
1
1
4
1
e/
1
=
= 1 + /
= 1 f ( )
+1
1 + e/
e
+1
Solution 3. Distribution function for double occupancy statistics.
(a) = 1 + e/ + 2 e2/ where = e/ .
f () = f ( + ) =
e/
hN i = ln =
/
e/ + 22 e2/
(e
+ 2e2/ ) =
P p/tau
Solution 4. Energy of gas of extreme relativistic particles. For p ' p, s e
= Z.
With the factor 2 for the 2 possible polarizations,
Z
Z
Z
4 2
p dpep/ = { p2 ep/ ( )
Z = (2)
2pep/ ( )} = 2
pep/ dp =
8 0
0
0
0
Z
p/
p/
3
== 2 { pe
( )
e
( )dp} = 2
hN i = ln =
ln Z
= 2 {ln (2 3 )} = 2 (3 ln ) = U = 3
Solution 5. Integration of the thermodynamic identity for an ideal gas. For constant N , recall
dU
pdV
1 U
1 U
pdV
d =
+
=
d +
dV +
V
V
U
CV = V , and for an ideal gas pV = N .
Z
Z
1 U
d = = CV ln + N ln V +
dV + 1
U
Now U = 23 for an ideal gas, so V
= 0.
U = 2
= = CV ln + N ln V + 1
1 independent constant of and V .
Solution 6. Entropy of mixing.
20
s /
s s e
Z
and
s
V
X
U
=
V
s
s
V
es / + s
U
V N .
es /
/Z
X s 1
X
es /
s2 es / /Z 2
V
s
s
2
Now p =
So if the system is in state s; then ps =
s
V N .
P
= hpi = p =
(b) Now s =
2 2
n ~
L2 2M
s
V N
es /
2 2
n ~
V 2/3 2M
s
V
N
2
n2 ~2
2
= V 5/3
=
s
3
2M
3V
(c)
2s s /
s 3V e
P
p=
Time for a large fluctuation.
nQ
5
(a) Recall = N [ln
n + 2 ]. nQ =
n
2V
+ 52 ]
f = N [ln QA
N
n
V
+ 52 ]
i = N [ln QA
N
Now
2
3
1
V
U
Solution 8.
M 3/2
.
2~2
N
5N
NQ
nQ N 5N
g e exp ln
+
=e 2
n
2
n
2
2
4
1c
(938 M eV /c )((0.8617 10 eV )/K)(300 K) 1 M eV
= 7.88 1030 /m3
nQ = 4
2(6.582122 1022 M eV s)2
106 eV
3 108 m/s
Now P V = N . Then
2
5
N/m2
(1 atm)( 1.01310
) kgm/s
1 atm
1N
N
P
=
=
= 2.445 1025 /m3
V
1.381 1023 J/K(300 K)
Now 1 L = 103 m3 and so for 0.1 L,
1
)(104 m3 ) = 2.445 1021
m3
7.88 1030 /m3
= 3.22 105
2.445 1025 /m3
(2.445 1025
With
21
= g e 2 (2.44510
21
(b)
(c)
Solution 9. Gas of atoms with internal degree of freedom.
For an ideal monatomic gas, assume noninteracting.
nQ =
M 3/2
.
2~2
ext = exp (/ ) or 1
M 3/2
Z1 is the usual canonical partition function, Z1 = nQ V where nQ = 2~
2
X
s
Z1 =
exp
)Z1 = (1 + e/ )Z1
( exp (s / )(1) + exp
s
(Z1 )N = ((1 + e/ )Z1 )N
21
(b)
(c)
Solution 10. Isentropic relations of ideal gas.
dp
+ dV = 0
p
V
d
( 1)
+
dV = 0
dp
d
+
=0
p
1
pi Vi
V ,
p
pi Vi
=
V
V +1
pi Vi
p
=
= p
= V
V
V
So that B = V (p/V ) = p, the isentropic bulk moduli.
P
n
B = V
=
=p
V
V
since
pV = n
n
p=
V
p
n
=
V
V2
7. F ERMI AND B OSE G ASES
Problems. Problem 1. Density of orbitals in one and two dimensions.
(a) Show that the density of orbitals of a free electron in one dimension is
D1 () = (L/)(2m/~2 )1/2 ,
(16)
(17)
independent of .
p2
2m
2
2
2
~2 (nx +ny )
2m
L2
n2 2
~2 2
2m
~
x
= s = 2m
for 2-dim.
L2 for 1 dim., s =
If F = Fermi energy, energy of the highest filled orbital,
n2
1-dim: N = 2nF . 2-dim.: N = (2) 14 (n2F ) = 2F
2 factor for 2 possible spin states.
1-dim: F =
2-dim: F =
~2
2m
~2
2m
1-dim.: D() =
N 2 2
1
~N 2
1
1
~m 2 2
n
N=
2
L2 = 2m
2
V 2 = 2m
2
2
mV F
2N
~2 N 2
~2 N
~2
= m V = m V = m n N = ~2
L
dN
d
2m
2V 2 1
1/2
~
2 (F )
N
2
2m 2 1/2
~
2-dim.: N = Am/~2
22
2mF
2V 2
~
Energy of relativistic Fermi gas. For electrons with an energy mc2 , where m is the rest mass of the
electron, the energy is given by ' pc, where p is the momentum. For electrons in a cube of volume V = L3 the momentum
is of the form (~/L), multiplied by (n2x + n2y + n2z )1/2 , exactly as for the nonrelativistic limit.
Problem 2.
(a) Show that in this extreme relativistic limit the Fermi energy of a gas of N electrons is given by
F = ~c(3n/)1/3 ,
(18)
where n = N/V .
(b) Show that the total energy of the ground state of the gas is
3
N F .
4
The general problem is treated by F. Juttner, Zeitschrift fur Physik 47, 542 (1928).
U0 =
(19)
Solution 2.
(a) ' pc =
~n
L c,
~
L
~nF
L c.
= (2) 81
F =
3N 1/3
= ~c
4
3
3 nF
3
3 nF .
nF =
3N 1/3
.
3n 1/3
(b)
Z nF
Z
~ 2 c 4
~ 2 c nF
1
2 ~nc
dnn
dnn3 =
=
n =
n = 2 4
U0 = 2
8
L
L
4L F
0
0
nnF
4
~ 2 c F L
~ 2 c 3N
F L
3
=
=
= N F
4L
~c
4L
~c
4
X
(a) Show that a Fermi electron gas in the ground state exerts a pressure
5/3
(3 2 )2/3 ~2 N
(20)
p=
5
m V
In a uniform decrease of the volume of a cube every orbital has its energy raised: The energy of an orbital is
proportional to 1/L2 or to 1/V 2/3 .
(b) Find an expression for the entropy of a Fermi electron gas in the region F . Notice that 0 as 0.
Solution 3.
2
~
(a) Recall U0 = 53 N 2m
(3 2 N )2/3 V 2/3
3 ~2
U
= N
(3 2 N )2/3
V
5 2m
2
3
V
5/3
1 ~2
=
(3 2 )2/3
5 m
N
V
5/3
So then
5/3
U0
1 ~2
N
2 2/3
p=
=
(3 )
V
5m
V
2 2/3
~2
3 N
and that the heat capacity of an electron gas is Cel = 12 2 N F =
(b) Recall that F F = 2m
V
helps directly with finding the entropy.
Z
Z
1
11 2
2 N
( ) (0 ) =
dU =
N d =
F
2F
0
0 2
U
,
which
Let (0 = 0) = 0,
( ) =
2 N
2F
Problem 4. Chemical potential versus temperature. Explain graphically why the initial curvature of versus is upward
for a fermion gas in one dimension and downward in three dimensions (Figure 7.7). Hint: The D1 () and D3 () curves are
different, where D1 is given in Problem 1. It will be found useful to set up the integral for N , the number of particles, and to
consider from the graphs Rthe behavior of the integrand between zero temperature and a finite temperature.
F
Solution 4. Recall, N = 0 dD().
23
1-dim:
1/2
Z
L
2m
L (2m)1/2 F
d
dD1 () =
N=
d1/2 =
=
~2
~
0
0
0
F
L (2m)1/2 1/2
L (2m)1/2 1/2
=
(2 ) =
2F
~
Z
F
F
3-dim:
F
Z
N=
0
V
d 2
2
2m
~2
3/2
1/2
V
=
2 2
2m
~2
3/2
2 3/2
3
3/2
F
V
2m
3/2
F
=
3 2 ~2
0
(a) For 3 He, given I = 1/2, density of liquid 0.081 g cm3 , we want to find vF , F , F .
2
~
F =
(3 2 n)2/3 =
2m
3
2/3
(6.582 1022 M eV s)2
1 kg
1u
1 He
2 0.081 g
3
=
=
2
cm3
103 g
1.67 1027 kg
3u
1c
2 3 938 M eV /c2 31010
cm/s
= 4.24 1010 M eV = 4.24 104 eV
Now suppose we have a nonrelativistic gas. Then 12 mvF2 or vF2 =
cm
vF = 1.675 104
sec
TF =
2F
m
4.24 104 eV
= 4.92 K
0.8619 104 eV /K
(b)
2 3N
2
2
D(F ) =
N
=
= 1.003kB T N
3
3 2F
2 F
Solution 6. Mass-radius relationship for white dwarfs.
(a)
Z
Z
G 4 r3 2
M
4 1
M
3GM 2
r dr = 4 4 3 G R5 4 3 =
U = (r)(r)r2 4dr = 4 3
r
3 5
5R
3 R
3 R
(b)
2
~
F =
(3 2 n)2/3
2m
is the Fermi energy.
With V = 34 R3 ,
2/3
1
h2 3 2 N
(3 2 )2/3 ~2 N 5/3
(3 2 )2/3 ~2
N 5/3
2
Ttot = N mv = N F = N
=
=
=
2
2m
V
2
m V 2/3
2
m 4 2/3 R2
3
9 2/3 2 5/3
5/3
~ N
2 (M/MH )
4
=
'
~
2
mR2
mR2
Cel =
since N =
M
MH
since MH m.
(c)
~2 M 5/3
5/3
mMH R2
GM 2
R
= M 1/3 R '
~2 /G
5/3
mMH
103 g
1 kg
2
/(6.67 1011
m3 /s2
)
kg
m2
;
s2
N m2
m3 /s2
m3 /s2
=
kg
=
kg 2
kg 2
kg
24
(3 108 m/s)2
1 c2
1024
g)5/3 (6.67
m2
s )
102 cm
1m
3
2
1011 mkg/s
2
103 g
1 kg
2
102 cm 3
)
1m
(3 1010 cm/s)2
1 c2
1020 g 1/3 cm
(d)
=
M
4
3
3 R
=
4
3
1020 g 1/3 cm
M 1/3
3 =
(2 1033 g)2
3 1066 g 2
M2
=
=
4
60
3
1060 g cm3
g cm3
3 10 g cm
4
60
3 10
106
g
cm3
(e)
M 1/3 R '
~2 /G
1017 g 1/3 cm
5/3
mMH
= R =
1017 g 1/3 cm
= 7.937 km
(2 1033 g)1/3
2.404V 3
2 ~3 c3
2 3 3 1/3
~ c N
=
2.404 V
N = Ne =
With a concentration of 1020 cm3 , T = 1.7 106 K (the critical temperature in K below which Ne < N .
Solution 8. Energy, heat capacity, and entropy of degenerate boson gas.
Recall that the distribution function for bosons is
1
f (, ) =
exp [( )/ ] 1
Consider N noninteracting bosons of spin zero.
1
= 0 for ground state. Thus, f (0, ) = exp
. Recall that
( )1
3/2
Z
Z
2M
1
V
N ( ) =
1/2 1
dD()f (, ) =
d 2
2
4
~
exp
0
0
1
Recall,
U =0
1
exp (/ ) 1
D()d =
e()/ 1
e()/
0
3/2 Z
2M
3/2
V
=
2
2
()/
4
~
e
1
0
V
1 4 2
2M
~2
3/2
V
4 2
2M
~2
3/2 Z
3/2
1
e/
x = /
dx = d/
V
= U =
4 2
2M
~2
3/2
5/2
Z
0
x3/2 dx
= B0 5/2 C0
ex 1
3/2
Z 3/2
V
2M
x dx
5
3/2
CV =
2 4 2 ~2
ex 1
0
Now
U V
.
V B0 25 3/2 C0 d
5
= V B0 C0
2
5 3/2
dU =V B0
C0 d
5 2
2= V B0 C0 3/2
2 3
0
Z
(U ) (U0 ) =
1
dU =
25
1/2 d =
1/2 d =
5
5
U 3/5
5
= (V B0 C0 )2/5 U 3/5 =
(U ) = V B0 C0 3/2 = V B0 C0
3/5
3
3 (V B0 C0 )
3
3/2 Z 3/2 !2/5
x dx
2M
5 3/5
V
U
=
x1
4 ~2
e
3
0
3/5
= 3/2 .
where we had used U = V B0 5/2 C0 or V BU0 C0
Solution 9. Boson gas in one dimension.
In one-dim.,
s =
= n =
~2 2 n 2
~2 2 n 2
2mV 2
=
or
s = n2
2m L2
2m V 2
~2 2
2mV 2
~2 2
1/2
1/2 =
dn
=
d
2mV 2
~2 2
1/2
1
21/2
D(n)dn =
N ( ) =
dD()f (, ) =
0
d
0
1
2
2mV
~2 2
1/2 Z
2mV 2
~2 2
1/2
1
1
exp
1=
1
1/2
2
d 1
(
exp
1)
1/2
3
N F
4
=
3 4/3
N ~c
2
2hT i = khU i
1/3
3
1
3GM 2
3GM 2
=
=
L
5R
5R
F = ~c
3n
1/3
4/3
=
GM 2
5R
2L
~ 2/3 c31/3
= N =
GM 2
5R
3
4
1/3
L=R
2L
~ 2/3 c31/3
3/4
=
2GM 2
5
41/3
~32/3 1/3 c
3/4
5~(32/3 ) 1/3 c
41/3 (2Gm2H )
3/2
=
2Gm2H
5
41/3
2/3
~3 1/3 c
3/4
N 1/2
!3/2
3/2
5(32/3 ) 1/3
= 2.2 1058
41/3 2
with = (U, V ) C ()
= (U, V ) C ()
Recall energy conservation in this form:
dU = W + Q
Consider pure heat and, so, no work. Now Q = d
(U is suited
Heat Engines: Conversion of Heat into Work. Consider curve c : R s.t. c generates vector field c =
c(t)
for this).
Q
=
This is whats meant when its said reversible heat transfer accompanying 1 unit of entropy is given by temperature [1].
Consider Figure 8.1 on page 229 of Kittel and Kroemer [1]. Roughly it looks like this:
= h
dh = Qh /h
Qh
= l
dl = Ql /l
Ql
R1
0
Legendre transforms revisited. Lets recall 2 of our favorite thermodynamic potentials, U , and Helmholtz free energy F .
They are related by Legendre transformations that transform 1 coordinate into its conjugate coordinate, somewhat like how
the Legendre transform transforms that Lagrangian in canonical coordinates into a Hamiltonian written with the conjugate
momentum. However, I do want to point out that, for Lagrangians and Hamiltonians, the Legendre transformation is a fiber
derivative between tangent bundle to the cotangent bundle on the manifold. In our current case, we want a mundane Legendre
transformation between convex function to another convex function, a coordinate transformation by a C function, not a
morphism between vector spaces.
Recall F . Its defined as such:
F U , so
dF = dU d d = d pdV
27
Consider curve c : R
c(t)
Consider 2 curves that generate vector fields:
c =
or c = V
d +
V
F
V
dV
Thus,
F
=
V
F
= p
V
=
V
So-called natural coordinates for F are , V . So 3 (, V ) (i.e. after a Legendre transformation, the coordinates become
(, V ) for each thermodynamic state.
Recall U as a thermodynamic potential. Using energy conservation and how Q is defined,
dU = Q + W = d + pdV
Natural coordinates are , V for U . So 3 (, V ).
heat engine
ideal heat engine:
(1 , V0 )
1
Qh = h dh
Ql = l dl
Qh = h dh
(0 , V0 )
W + Ql = Qh or W = Qh Ql
h l
W = Qh Ql
Qh = C Qh
h
Carnot efficiency C
h l
h
Ql = l dl
(2 , V1 )
l = h so
Qh
Ql
=
h
l
is the ratio of the work generated to the heat added, in the reversible process.
Carnot cycle.
3
W23
(H , l )
W34
W12 = Qh
4
W41
W23
(H , h )
W34
(L , l )
W12 = Qh
(L , h )
W41
H
The total work is as such: dU = 0 for 2 reasons: mathematically, the integration of an exact 1-form around a closed curve
is 0, and physically, we return the system back to its original state, as this is a reversible process.
I
I
I
I
I
dU = 0 = d pdV = W = d = [h (H L ) + 0 + l (L H ) + 0] = (h l )(H L )
28
(H , l , V3 )
W34 = Ql
W12 = Qh
(L , l , V4 )
W41
(H , h , V2 )
W34 = Ql
W12 = Qh
4
W23
(L , h , V1 )
W41
with
isothermal expansion Qh = W12 =
pdV = N h ln
V2
V1
l V31
dU = U (h ) U (l ) = CV (h l )
h V21
isothermal compression Ql =
W34
pdV = N l ln
=
3
V3
V4
EY : 20150911 I dont have a good reason why CV which is defined for constant V , that CV
isentropic (i.e. adiabatic) expansion from 2 3.
The total work done is
V2
W = N (h l ) ln
V1
Energy Conversion and the Second Law of Thermodynamics.
W1 = 1 Qh
11
Qh
h
l
1
1
V4
h 1
= ( ) 1
V1
l
Ql1 = (1 1 )Qh
V3
or
=
V2
U
V
Wout = 2 Qh 1 Qh
12
Qh
Qh
01
Ql2
02
Q(in) = (2 1 )Qh
Ql2 = (1 2 )Qh
11
Wout
12
Qh
01
02
Q(in)
Ql2
So with Q(in) heat in, Wout net work can be done. But thats a decrease in overall entropy. This violates the law of increasing
entropy.
29
Define H = U + pV . H C (), where is the manifold of equilibrium (and non-equilibrium) states of the system.
Path Dependence of Heat and Work. Mathematically, Q and W are not necessarily exact 1-forms. So they are path-dependent.
EY : 20150911 That Q, W are not necessarily exact 1-forms would imply that has some nontrivial, interesting topological
features.
Heat and Work at Constant Temperature or Constant Pressure.
isothermal work.
dU = W + Q = W + d
F = U
dF = dU d d = W d
If d = 0, on an isothermal curve,
dF = W , W becomes an exact 1-form, with potential function F , the Helmholtz free energy.
isobaric heat and work. e.g. boiling of liquid. When liquid boils under atmospheric pressure, vapor pressure displacing
atmospheric odes work against atmospheric pressure. isobaric process.
Consider this change of volume:
dx = dV
A . Now
peq = vapor pressure.
F = peq A = patm A (force equilibrium)
(1 , V1 )
W = patm Adx = patm dV
(0 , V0 )
W = patm dV pdV = d(pV ) is part of total work done on system.
If d(pV ) > 0, work provided by environment and is free.
If d(pV ) < 0, work delivered to environment and not extractable from system for other purposes.
W + d(pV ) = dU Q + d(pV ) = dH Q
Recall that for enthalpy H = U + pV ,
dH = dU + V dp + pdV = dU W + V dp = d + V dp
, p are natural coordinates of H.
dH Q = W + d(pV )
An isobaric curve s.t. dp = 0,
dH = Q + W + d(pV )
so
Q + W is an exact 1-form of H pV = d(H pV ) = W + Q.
2 classes of constant pressure processes:
(a)
W + d(pV ) = 0
dH = Q
e.g. liquid evaporation from open vessel, because no effective work is done.
heat of evaporation is enthalpy difference between vapor phase and liquid phase
(b) constant temperature and constant pressure.
G = F + pV = U + pV
dG = dF + V dp + pdV = dU d d + V dp + pdV = V dp d
dG = W d + d(pV ) = W + d(pV ) d
with natural variables are p,
at constant temperature, W + d(pV ) is exact 1-form, dG
30
Qh
h
>
Ql
l
or
l
h Qh
> Ql ,
l
h Qh
Qh
Qh Ql
W
=
<
= c, ideal
Qh
Qh
Qh
(b) Qh = electricity consumed by reversible heat pump.
hh
Carnot engine: W = (hh l )(hh l ), with hh = Qhh
, and l = Qll
Condition that electricity consumed by reversible heat pump:
Qhh
Ql
W = (hh l )
= Qh
hh
l
Note we let l = Qll since both heat pump andCarnot engine are reversible.
Qhh
Qh
Qh
Qhh
1
Qhh
hh (h + hh l )
1
=
=
=
= Qh
+
=
=
hh
h
hh l
hh
hh l
h
Qh
h (hh l )
For Thh = 600 K, Th = 300 K, Tl = 270 K,
600(300 + 600 270)
Qhh
=
= 3.82
Qh
300(600 270)
(c) See Figure (1).
Solution 2. Absorption refrigerator.
=0
=
hh
l
h
Qhh
Ql
Qhh + Ql
1
1
1
1
+
=
or Qhh
= Ql
hh
l
h
hh
h
h
l
Ql
Ql
1
1
1
1
h hh
l h
hh h
l
=
=
/
=
=
Qhh
hh
h
h
l
h hh
h l
h l
hh
Qhh
Note that Ql Qh = Ql (Qhh + Ql ) = Qhh ; weve removed Qhh heat from refrigerators inside.
31
~
i .
= s = pc = ~ks c =
~c.
Recalling that there are 2 polarization states for a photon in 3-dim. space,
Z
Z
n n
2 ~c 3
~c
1
L ~c/
2
~c e
=
n dnexp
n =
U = (2)
(4)
n dn
8
L
L
L
0
0
2
Z
L
~c
L
~c
~c
2
3
n
3n exp
n
=
{ n exp
dn} =
L
L
~c 0
L
~c
0
2
Z
~c
K
~c
n dn} =
=
{(1)
3
n2 exp
L
~c
L
0
2
Z
~c
~c
L
~c
L
L
2nexp
=
{(1)
3{ n2 exp
n
n
dn =
L
~c
L
~c 0
L
~c
0
2
2
Z
~c
L
L
~c
2
=
(1)
3(2)
n
dn =
nexp
L
~c
L
~c
0
2
3
2
4
Z
~c
L
~c
L
~c
~c
=
(1)3
3(2)(1)
n dn =
(1)3
3(2)1 exp
n =
exp
L
~c
L
L
~c
L
0
0
3
L
V
=6
4 = 6 2 3 4 = U
2 ~c
( ~c)
= 1 , and using this is usually the most direct way to obtain entropy.
To get the entropy, recall, U
V
Solution 3.
ns
L
dU
=
= d =
6V
( 2 ~2 c)3
4 3
d
6V
1
8V 3
= 2 2 3 3 = ( ) = 2 2 3
( ~ c) 3
( ~ c)
Consider
Isothermal expansion: Helmholtz free energy F is needed.
F = U =
Then
p=
F
V
=
, N
W12 = p(V2 V1 ) =
6V
8V 3
2V 4
4
( 2 ~2 c)3
( 2 ~2 c)3
( 2 ~2 c)3
2 4
( 2 ~2 c)3
2h4
(V2
2
( ~2 c)3
Isentropic expansion: = V2 h3 = V3 l3 or V3 = V2
So for this isentropic process,
V2 h3
Q12
V1 )
h
l
8h3
(V2 V1 )
( 2 ~2 c)3
8 4
= = 2 2h 3 (V2 V1 )
( ~ c)
12 =
3
=V ,
U=
6V
( 2 ~2 c)3
V2 h3
V
4/3
=
32
W23
8l3
( 2 ~c)3 (V4
V3 ) =
U
6(V2 h3 )4/3
=
V
( 2 ~2 c)3
2l4
( 2 ~2 c)3 (V4
8h3
( 2 ~c)3 (V1
V3 ) =
W =
6(V4 l3 )4/3
=
( 2 ~2 c)3
6V2 4
2h4
(V2 V1 )+ 2 2 h 3
2
2
3
( ~ c)
( ~ c)
1 4/3
V
3
2h3 l
( 2 ~2 c)3 (V1
1
1/3
V3
1
1/3
!
=
V2
V2 ).
V2 ).
Isentropic compressiong: V4 l3 = V1 h3 or V4 = V1
W41
h
l
3
1
1/3
V4
.
1
1/3
V1
!
=
6V1 h4
( 2 ~2 c)3
1
l
h
l
6V1 4
l
l
2 3 l
8 4 (V2 V1 )
1
+ 2 h2 3 (V1 V2 )+ 2 2 h3 1
= h 2 2 3
h
( ~ c)
( ~ c)
h
( ~ c)
h
1
Qh =
W
8h4 (V2 V1 )
l
=
=1
( 2 ~c)3
Qh
h
Solution 4. Heat engine-refrigerator cascade. Consider the heat engine as a Carnot cycle.
W + Wr = (h l )h
where Wr = work consumed by refrigerator.
Qh
Ql
=
= l
h
l
This must be true for any heat engine undergoing Carnot cycle; furthermore, we can say its the most efficient heat engine
possible.
reversible refrigerator: QL + Wr = QH , (by E-consv.)
L = H = QLL = QHH , (by reversible condition)
Note, Ql is energy transfer from heat engine to l reservoir. QL is energy transfer from l reservoir to refrigerator. QL Ql ,
otherwise, no cooling, no thermal energy extracted from l resevoir to lower its temperature. QL = Ql at equilibrium; no
further cooling, r reached.
Note that l is given as the environmental temperature. Assume refrigerator throws out QH heat into the environment.
H = l . Since QL heat inputed into refrigerator from a l reservoir now lowered to r , l r .
l
l
Wr = QL QL =
1 QL
r
r
h =
r
1
h
QL
L
QH
H .
l
QL
r
l
r
l
1
= 1
1
= 1
r
Qh
h
r
h
h
(a)
Ql
h
W = (h l )
=
1 Ql
l
l
h
dQl
h
P
P =
1
=
1 A(h l ) = l = (h l )(h l ) = h2 2h l + l2
l
dt
l
A
= l2 2h l
P
l = h +
2A
P
l + h2 = 0
A
r
(h +
P 2
) h2
2A
(2 kW )(290 K)
580 103 W
W
P l
=
=
= 1450
(h l )2
(310 290)2
400 K
K
h
l
1 Ql = 1
Qh
l
h
Carnot refrigerator expels Qh thermal energy to hot h environment and inputs Ql thermal energy from l reservoir.
Ql + W = Qh
Work W must be drawn by Carnot refrigerator to do work. Suppose Carnot cycle part of the refrigerator must input in heat
from light bulb to cool down its inside, i.e. consider Carnot refrigerator in equilibrium with light bulb, now inputting in heat
from light bulb Qext , and drawing in work to expend out Qh thermal energy into the environment.
= Qext = Ql
= Q l in this case, so
W
h
h
1 Ql Ql = 0 or
2 Ql = 0
l
l
= l =
300 K
h
=
= 150 K
2
2
Given Qh = M CdTh ,
Tl lower reservoir temperature stays constant. h decreasing, dh < 0.
Qh
l
dh
W = (h l )
= 1
(M C)
h
h
kB
MC
MC
i
= W =
(h l ln h )|fi =
l ln
(i f )
kB
kB
f
For M = 1017 g, C = 1 J/g K, Tl = 20 C = 293 K, Ti = 600 C = 873 K, Tf = 110 C = 383 K
W = 2.486 1019 J
3600 sec
Ql
=
l
U
T V
h
1
a h
a
1 (al3 dl )
=
1
l3 dl = 4 (h l2 l3 )dl
4
4
l
kB
kB l
kB
0
a
1
1
aTh3
W = 4 h l3 l4 =
=W
kB
3
4
12kB
h
34
(a)
G
G
=
=V
N, p
p
V
2
=
=
2
G
V
p
p
G
=
=
p p
p
p
p
G
G
=
=V
N p
p
V
2
=
=
2
V
G
N p
p N
G
=
=
N
p
N
pN N
p N
p
p
2
2
=
=
=
=
N N
N
N
N
N
N
1
= 0 as 0 since constant as 0 by third law of thermodynamics.
(b) = V1 V
p = V
p
[e][H + ]
= nQ eI/
[H]
[e]
= 62
[H(exc)]
Solution 4. Biopolymer growth.
j ln nj =
j ln cj =
ln nj j =
ln cj j = ln
nj j = K( )
nj j = ln K( )
[ monomer][N mer]
[(N +1)mer]
[1][N ]
[N +1]
= KN .
[1]3
[1]2 [1][2]
=
= K1 K2
[2] [3]
[3]
[1][1]
= K1
[2]
= [N + 1] = [1]N +1 /K1 K2 K3 . . . KN
j
j+1
Y
[1]j+2
[1]j+1 [1][j + 1] Y
=
Kl Kj+1 =
=
Kl
[j + 1] [j + 2]
[j + 2]
l=1
l=1
nQ (N )nQ (1)
FN
F1
(FN + F1 FN +1 )
FN +1
nQ (N )nQ (1)
=
exp
exp
exp
=
nQ (N + 1)
nQ (N + 1)
3/2
N
where nQ (N ) = M
and MN is the mass of N mer molecules, FN is the free energy of one N mer molecule.
2~2
(c) Assume N 1 so nQ (N ) ' nQ (N + 1). Assume [1] = 1020 cm3 . Assume F = FN +1 FN F1 = 0,
meaning zero free energy change in the basic reaction step. Were given the molecular weight of the monomer to be
200.
M1 3/2
We want [N[N+1]
.
] at room temperature. Now KN ' nQ (1) = 2~2
[1][N ]
= nQ (1) =
[N + 1]
Note that
M1
2~2
3/2
or
[1]
[N + 1]
=
=
[N ]
nQ (1)
2(6.5821022 M eV s)2
200(938M eV /c2 )(0.8617104 eV /K)(298 K)
31010 cm/s
1c
2 3/2
2~2
M1
3/2
[N + 1]
= 3.627 108
[N ]
[N + 1]
[1]
=
exp
[N ]
nQ (1)
= F < ln
or ln
nQ (1)
F
<
[1]
[1]
= 0.44 eV
nQ (1)
36
1020 cm3
Let C (N )
be a smooth function on N .
= (t, x) locally
Let J 1 (N ) be a 1-form on N that is isomorphic to J (Tangent-Cotangent isomorphism theorem), i.e.
J = J[
Ji = gij Jj
with gij being the metric on N (not just M !)
Note that as N = R M , g0j = 0j
The local form of J is the following:
J=
+ ji i
t
x
i = 1...n
So
J = Ji dxi = gij Jj dxi = dt + jk dxk
k = 1...n
Thus
J = dt + jk dxk
(21)
k = 1...n
g 0
dxi dxin
i1 . . . in {1 . . . n}
n! i1 ...in 1
g
k
dxi1 dxin = ij voln+1
jk dxk = gkl j l
(n + 1)! i1 ...in
dt =
so thus
J = voln + ij voln+1
Hence
dJ =
(22)
Special case:
g
t
1
1
( g) voln+1 +
( gjk ) voln+1 = d(voln ) + dij voln+1
k
t
g
x
g
=0
jk
ln g jk voln+1 +
voln+1 = 0
k
x
xk
jk
+
ln
=0
g
jk +
=
t
xk
xk
n+1
dJ =
vol
+
t
jk
Special case: if g constant,
t + xk = 0
Let j Dd (j is a closed form on M ) where d =
i
xi dx
i = 1 . . . n, D constant
d J = dvoln + Dd d = 0
37
g constant,
2
=D
t
(xk )2
+ ji i
t
x
Let J = J[ . J = g J
For special case of flat Minkowski space,
J = dt + ji dxi
J = dt + ji dxi
g
g
0
i1
in
dx dx + ji
i
dx1 dxn
(n + 1)! i1 ...in
(n + 1)! 1 ...n
( g) 1
(ji g) 1
n+1
dJ =
+
vol
voln+1 = 0
t
g
xi
g
( g) (ji g)
=0
=
+
t
xi
Fick law (14.19) for particle flux density, j = Dn dn where Dn
n
J = ndt + j
b
thermal conductivity; homogeneous medium C heat capacity per unit volume. ju = Kd
b dt + ju
J = C
(23)
(24)
b + (ju )k = 0
C
t
xk
2
= D
t
(xk )2
(5)
b
D K/C
(6)
(27)
pV = N or p = /M
(28)
Consider solid ball or billiard ball particle (extended particle, not pt. particle, but no internal structure)
NM
=
V
Force on particle
Z
Z
Z
dP
d
M
M
u
n
F =
=
vol u =
L +u u =
+ [u, u]
t
dt
dt
V
V
t
Suppose [u, u] = 0 (certainly for flat spaces; what about for curved spaces? [u, u] 6= 0? Possibly? I dont know. EY:
20150317
(27)
dU + pdV = d
= 0 (1 + s)
= 0 (1 + )
(5)
(30)
k
k
u
s
=0
M
M
s ku = 0
(40)
(31)
bV ps = 0 or C
bV ns = 0
C
(29)
(39)
(41)
k
n
u =
1+
s
bV
M
C
k
n
k
=
1+
b
M
CV
So
=
(32)
1/2
M
(42)
bV + n
bp
C
C
=
bV
bV
C
C
1/2
vs =
=
k
M
=
(x, 0) = (x) =
(33)
(x, t) =
(34)
1
2
1
2
dk exp (ikx)
(58)
(59)
(35)
1
(x, t) =
2
(36)
(10)
dk exp [ikx Dk 2 t]
(60)
(37)
x2
4Dt
(14)
(a)
2
r 2 2
2
= +
t
t
4 Dt2
2
2
1 2
1 2
1 2
=
+
(x2 + y 2 )
(xi )2
2 Dt 2 Dt 4 D2 t2
=
2
2 2
=D
t
(xi )2
(b)
(c)
39
R EFERENCES
[1]
[2]
[3]
[4]
Charles Kittel, Herbert Kroemer, Thermal Physics, W. H. Freeman; Second Edition edition, 1980. ISBN-13: 978-0716710882
Bernard F. Schutz, Geometrical Methods of Mathematical Physics, Cambridge University Press, 1980. ISBN-13: 978-0521298872
Paul Bamberg and Shlomo Sternberg, A Course in Mathematics for students of physics: 2, Cambridge University Press, 1990.
T. Frankel, The Geometry of Physics, Cambridge University Press, Second Edition, 2004.
There is a Third Edition of T. Frankels The Geometry of Physics [4], but I dont have the funds to purchase the book (about
$ 71 US dollars, with sales tax). It would be nice to have the hardcopy text to see new updates and to use for research, as the
second edition allowed me to formulate fluid mechanics and elasticity in a covariant manner. Please help me out and donate
at ernestyalumni.tilt.com or at subscription based Patreon, patreon.com/ernestyalumni.
E-mail address: ernestyalumni@gmail.com
URL: http://ernestyalumni.wordpress.com
40